CHAPTER 2

2.0 ATOMIC STRUCTURE

2.3. ELECTRONIC
2.1. BOHR’S
CONFIGURATION
ATOMIC MODEL

2.2. QUANTUM
MECHANICAL MODEL
 2.1 Bohr’s Atomic Model
At the end of this topic students should be able to:-
a) Describe the Bohr’s atomic model.
b) Explain the existence of electron energy levels in
an atom.
c) Calculate the energy of electron using

– RH 1
En =
n2
RH = 2.18 x 10-18 J

d) Describe the formation of line spectrum of

hydrogen atom.
 2.1 Bohr’s Atomic Model
At the end of this topic students should be able to:-
e) Illustrate the formation of Lyman, Balmer, Paschen,
Brackett and Pfund series.

f) Calculate the energy change of an electron during transition

∆ E = RH (1/ni2 - 1/nf2), where RH = 2.18 x 10-18 J

g) Calculate the photon of energy emitted by an electron that

produces a particular wavelength during transition;
∆ E = hv , where v = c/λ
 2.1 Bohr’s Atomic Model
At the end of this topic students should be able to:-
h) Perform calculations involving the Rydberg equation.
1/λ = RH (1/n12 - 1/n22), n1<n2
RH = 1.097 x 107m-1

i) Calculate the ionisation energy of hydrogen atom from Lyman series.

j) State the limitation of Bohr’s atomic model.

k) State the dual nature of electron using the Broglie’s

postulate and Heisenberg’s uncertainty principle.
 Historical of atomic model
460 BC ‘... he pounded up materials in his
pestle and mortar until he had
reduced them to smaller and smaller
particles which he called ATOMA

‘.. suggested that all

matter was made up
460 BC Democritus of tiny spheres that
were able to bounce
around with perfect
elasticity and called
them ATOM
John Dalton (1766-1844)
 Historical of atomic model
found that atoms could sometimes
eject a far smaller negative particle
which he called an ELECTRON

He suggested that the positive

charge was all in a central nucleus.
Joseph John Thomson
With this holding the electrons in
(1856-1940)
place by electrical attraction

Ernest Rutherford
(1871-1937)

Bohr refined Rutherford's idea by adding that the

electrons were in orbits. Rather like planets
orbiting the sun. With each orbit only able to
Niels Henrik Bohr
(1885-1962)
contain a set number of electrons.
2.1
BOHR'S ATOMIC MODEL
 THE BOHR MODEL OF THE ATOM

I pictured the electrons

orbiting the nucleus
much like planets
orbiting the sun.
However, electrons are
found in specific
circular paths around
the nucleus, and can
jump from one level to
another.
Niels Bohr
First Bohr’s Postulates:
Electron moves in circular orbits around the nucleus. Its only orbit
in certain radii in H atom. H atom has only certain allowable energy
level known as ‘stationary states’
[ orbit = stationary state = energy level = shell ] has same meaning

e-
H
Nucleus
1H
(proton) 1 n=3
n=1 n=2

* In moving in the orbit, the electron does not radiate

any energy and does not absorb any energy
Niels Henrik Bohr (1885-1962). Danish physicist..
Second Bohr’s Postulates:
The energy of an electron is quantised

Electron moving in an orbit can have only a certain discrete amount of energy

1 In this case, n=1.

En = – RH Unit for energy (E) is Joule
n2

n=1 When an electron (e) is infinite distance from

e -1 nucleus it has zero interaction with nucleus. As
it circulate near to the nucleus and have
n=3 stronger interaction it does some work and
releases some energy. Thus the energy of the
n=2 electron decreases and becomes negative
The idea that energy should be quantized or “bundle”
has many analogies

The eggs laid by hens

are quantized

A pregnant rabbit gives birth to an

integral number of rabbit, not one–half
or three–quarters of a rabbit
 THE BOHR ATOM

➲The energy of an electron in its level is given by:

 1 
E n  R H  2 
n 
RH (Rydberg constant) = 2.18 x10-18 J.
n (principal quantum number) = 1, 2, 3 ….∞ (integer)
 1
En = – RH
n2

n is associated with the radius of the orbit

* directly related to the energy of 1 electron at each n
n↓ E level lower

Negative sign: E = 0 when n = ∞ (free electron)

*n infinitely is farthest from nucleus
* Removing/ donating electron is remove e from outermost
shell to n ∞
Eelectron in atom < Efree electron

n↓ (more close to nucleus)

E more negative, stronger attraction towards nucleus
Try this…..
Calculate the energy of an electron when
it occupies a level equivalent to the
quantum number of n = 3

Answer :
At n = 3,
E3 = - RH = -2.18 x 10 -18

n2 33
= -2.42 x 10 -19 J
Ground state and excited state

Ground state
The most stable state. At ordinary conditions the electron is
at the ground state (lowest energy level).

Excited state
At excited state the electron has higher energy level
than at the ground state (unstable state)
GROUND STATE EXCITED STATE
When n = 1 When n = 2,3, …..
The lowest allowed Higher energy than the
energy state ground state
The most stable Stability of the electron
energy state decrease
The electron closest
to the nucleus

1
En = – RH
n2
Third Bohr’s Postulates:

* If energy is supplied, electron absorbed the energy and is

promoted from a lower energy level (ground state) to a
higher n called excited state.

n=1 A specific amount of energy is absorbed

∆E = hv = E3-E1 (+ve)
n=3

n=2
Energy level diagram for the hydrogen atom

n=
n=∞
n=4
n=4
n=3
n=3
n=2
n=2
Energy absorbed by electron
(+ve sign)
∆E = hv = Efinal-Einitial (+ve)
n=1
Third Bohr’s Postulates:
Electron at its excited states is unstable.

It fall back to lower energy level and released a specific amount of energy
in the form of photon (light) with produce certain wavelength.

•The energy of the photon equals to the energy difference between the
levels.

From this third postulate of Bohr’s, it explain how emission of

spectrum can produce series of lines.
Example pathway transition of electron of hydrogen atom forming photon:
n=1 (electron in hydrogen atom at ground state)
n=3 (electron in hydrogen atom at excited state)
n=2 (electron in hydrogen atom at lower state

n=3
e
n=1
e e
n=2

n1 to n3 : electron absorb energy

n3 to n2 : electron release energy in form of photon
Energy level diagram for the hydrogen atom

n=∞

n=4
n=3

n=2
Energy Energy
absorbed Released
(+ve sign) (-ve sign)
n=1
 THE BOHR ATOM
➲Radiant energy emitted when the electron moves from higher-energy
state to lower-energy state is given by the difference in energy between
energy levels:

∆E = Ef - Ei where
 1 
E i  R H  2 
 1    1   ni 
E  R H  2     R H  2  
 
 f  
n  i 
n
 1 
Thus,
E f  R H  2 
 nf 
 1 1 
E  R H  2  2 
 ni nf 
 THE BOHR ATOM
➲The amount of energy released by the electron is called a photon of
energy.
➲A photon of energy is emitted in the form of radiation with appropriate
frequency and wavelength.

where;
∆E = h v h (Planck’s constant) =6.63 x 10-34 J s
v = frequency

Where;
c c (speed of light) = 3.00x108 ms-1

 λ = wavelenght

Thus, hc
ΔE 

 1 1
∆E = RH = hv
ni 2 nf 2

∆E value can be positive (absorption) or

negative (emission).

But for the formula ∆E = hv, use

magnitude of ∆E (positive value)
because h and v values are always
positive!
 Points to Remember
Ground state
the state in which the electrons have their lowest
energy

Excited state
the state in which the electrons have shifted from
a lower energy level to a higher energy level

Energy level
energy associated with a specific orbit or state 26
 BOHR’S ATOMIC MODELS
1. Electron moves in circular orbits about the nucleus.
In moving in the orbit, the electron does not radiate any
energy and does not absorb any energy.
2. The energy of an electron in a hydrogen atom is
quantised, that is, the electron has only a fixed set of
allowed orbits, called stationary states.
3. At ordinary conditions the electron is at the ground
state (lowest level). If energy is supplied, electron
absorbed the energy and is promoted from a lower
energy level to a higher ones. (Electron is excited)
4. Electron at its excited states is unstable. It will fall back
to lower energy level and released a specific amount
of energy in the form of light. The energy of the photon
equals the energy difference between levels.
Example:
What is the energy of photons of monocromatic radiation with
the wavelength of 250 nm?

∆E = hv = hc


= 6.63 x 10 -34 J s x 3.00 x 10 8 ms-1

2.5 x 10 -7 m
= 7.956 x 10 -19 J
Example
Calculate the energy required to promote an
electron from the first energy level to the
third energy level of a hydrogen atom.
 1 1 
E  R H  2  2 
 ni nf 

 1 1 
 2.18x1018  2  2 
1 3 
 
= + 1.94 x 10-18 J
Example

Which of these electron transitions correspond

to absorption of energy and which to emission?

a) n = 2 to n = 4
b) n = 3 to n = 1

ANSWER:
a) Absorption energy
b) Emission energy
Explanation

a) n = 2 to n = 4
Electron transition: lower to higher level of n
Absorption energy

b) n = 3 to n = 1
Electron transition: higher to lower level of n
Emission energy
 Example

The electron in a ground–state H atom absorbs a photon of wavelength

97.20 nm. To what energy level does the electron move?

 1 1 
E  R H  2  2 
∆E = hv = hc  ni nf 


= 6.63 x 10 J s x 3.00 x 10
-34 8 ms-1
97.20 x 10 -9 m
= + 2.046x 10 -18 J
EXAMPLE:

a) The energy (in J) of an electron has when it occupies a level

equivalent to the quantum number of n = 3 and n = 4.

b) The energy (in kJ/mol) of photon emitted when one mole of

electron drops from the 4th energy level to the 3rd energy level.

c) The frequency (in s-1) and wavelength (in nm) of this photon.
 Answer
a) Energy of an electron at n = 3 (E3) :
1
E3 = – RH
n32
1
= – 2.18 x 10–18 J x
32
= – 2.42 x 10–19 J

Energy of an electron at n = 4 (E4) :

1
E4 = – RH
n42
1
= – 2.18 x 10–18 J x
42
= – 1.36 x 10–19 J
 Answer
b) Ephoton = ∆E = Ef – Ei (for one electron, n4 – n3)
= E3 – E4
= – 2.42 x 10–19 J – (– 1.36 x 10–19 J)
= – 1.06 x 10–19 J / electron

For 1 mol of electrons:

– 1.06 x 10–19 J 6.02 x 1023 electrons

∆E = x
1 electron 1 mol
= – 6.382 x 104 J/mol
= – 63.8 kJ/mol
 EXAMPLE – 05
Answer 3.1

c) ∆E = – 1.06 x 10–19 J
= hv
∆E
v =
h
1.06 x 10–19 J
= = 1.60 x 1014 s–1
6.63 x 10–34 J•s
c
λ =
v
3.00 x 108 ms–1
=
1.60 x 1014 s–1
 EXERCISE
Calculate the energy of an electron in the hydrogen
atom when n = 2, and when n = 6.
Calculate the wavelength released when an electron
moves from n = 6 to n = 2.
If this line in the visible region of electromagnetic
spectrum?
(Note: visible light: 400 ~ 700 nm)
ANS:
E2 = – 5.45 x 10–19 J
E6 = – 6.06 x 10–20 J
∆E = – 4.84 x 10–19 J
λ = 410 nm (visible light)
 EXAMPLE
“The energy of an electron in an atom is quantized.”
Describe the above statement.

Answer

•An electron at a certain distance from the nucleus

can only have a specific amount of energy.

•An electron has a certain energy level,which

corresponds to the number of the particular orbit.

•An electron can only exist on specific orbits and

not between orbits.
 Emission Spectra
An emission spectrum is the range or array of wavelengths (spectra) obtained when the light
emitted by a substance is passed through a prism and examined directly with a spectroscope.

Two type

Continuous Line
Spectra Spectra
 THE DIFFERENCES BETWEEN THE
CONTINOUS SPECTRUM AND LINE SPECTRUM
How the hydrogen spectrum formed ?
 Hydrogen gas is filled in a gas discharge tube.
Electric spark is passed through hydrogen gas:
H2(g) → 2H(g)

The energy supplied is absorbed by the electron of H atoms .

It caused them to be promoted from ground states to higher energy level.

These electrons are unstable at their excited states .

It will fall to lower energy level and emit light with particular wavelength.

These is how hydrogen spectrum is formed

VARIOUS SERIES IN ATOMIC
HYDROGEN EMISSION
 Energy level diagram of Balmer series

The first four emission photon at n=2 When the electrons

at excited state fall
n=∞ back to lowest
n=6
n=5 energy levels, radiant
n=4 energies (photons)
are emitted in the
n=3 form of light
(electromagnetic
radiation of a
n=2 particular frequency
or wavelength)

n=1
Two type diagram represent
Emission series of hydrogen atom
Energy level diagram

(Lyman series)
Energy level diagram Vs line spectrum diagram
n=∞
n=5
n=4

Energy n=3

n=2

n=1 st rd Emission of photon

1 line 2nd line 3 line

Line ∆E
spectrum λ
n2 – n1 n3 – n1 n4 – n1
st nd
1 line of lyman 2 line of lyman 3 rd line of lyman
 Which line is 1st line?

Convergent limit 1 st line

Ist line can be detect by pick the line far apart from
other lines. Can be on the left or on the right of line
Spectrum diagram.
 Ultraviolet Visible Infrared

➲The farther they fall, more energy is released and the higher the frequency.
➲This is a simplified explanation!
➲The orbitals also have different energies inside energy levels.
 EXAMPLE
A B C D E ∆E
Line
spectrum v

Specify the increasing order of the radiant energy, frequency and

wavelength of the emitted photon.

Which of the line that corresponds to

i) 1st line ? Line A

ii ) the shortest wavelength? Line E

ii) the lowest frequency? Line A

iii) highest energy Line E

 EXAMPLE

E D C B A Paschen series
Line
spectrum

Which of the line in the Paschen series corresponds to the longest

wavelength of photon?
Describe the transition that gives rise to the line.

Answer
Line A.
The electron moves from n=4 to n=3.
 EXAMPLE
W Y Balmer series
Line
spectrum

Describe the transitions of electrons that lead to the lines W,

and Y, respectively.

Answer
For W: transition of electron is from n=4 to n=2
For Y: electron shifts from n=7 to n=2

51
 RYDBERG EQUATION
Used calculate wavelength of any line in
a given series:

1 ( 1 1 )
= RH , n1 < n2
λ n12 n22

λ: wavelength of a spectral line (unit: m)

n: 1,2, 3 …..∞ (n>0)
RH: Rydberg constant = 1.097 x 107 m–1
 EXAMPLE

Use the Rydberg equation to calculate the

wavelength (in nm) of the forth line in the Balmer
series of H spectrum .

Which one is fourth Balmer series?

 Answer

Balmer series, electron: higher level to n = 2

4th line of Balmer: Transition n6 to n2

By using Rydberg equation:

1 ( 1 1 )
R
= H n1 < n2
λ n12 n22

= 1.097 x 107 m-1 1 1

22 62
= 2.438 x 106 m-1

Therefore, λ = 4.102 x 10-7 m = 410.2 nm

 EXERCISE

Use the Rydberg equation to calculate the

wavelength (in nm) of the photon emitted when
a hydrogen atom undergoes a transition from
n = 5 to n = 2.

ANS:
434.17 nm
 Compare the difference:
1 1
∆E = RH RH = 2.18 x 10–18 J
n2i n2f

1 1 1
= RH RH = 1.097 x 107 m-1
λ n12 n22 ,n1 < n2

n1 can be ni or nf as long as n1 < n2 to get positive value for λ

Both equations can be used to calculate wavelength (λ) and

frequency (v) of any line of H atom emission series

Remember! RH values and units are different in

both equations. Don’t switch !
 EXAMPLE

An electron in the n = 5 level of an H atom

emits a photon of wavelength 1281 nm.
To what energy level does the electron
move?

Clues
emits a photon : transition electron from higher (n5) n to lower n<5
 Answer

Electron transition: ni = 5 nf = ?

By using Rydberg equation:

1 1 1
= RH n1 < n2
λ n12 n22

1
= 1.097 x 107 m-1 1 1
1281 x 10–9 m n12 52

n12 = 8.996

n1 = 3
 EXERCISE

The electron in a ground–state H atom absorbs

a photon of wavelength 97.20 nm.
To what energy level does the electron move?

ANSWER :n = 4
EXAMPLE

Last line of hydrogen spectrum in Lyman series is when n∞ fall to n1

Calculate what is;
i ) Wave number
ii ) Wavelength
Iii ) Frequency
 ANSWER

1 1 1
i) =1.097 x 107 2 = 1.097 X 107 m-1
λ 12 ∞

ii) λ = 1 / wave number

= 1 / 1.097 X 107 m-1
= 9.116 x 10-8 m

iii) V = c =3.00 X 108 ms-1

= 3.29 X 1015 s-1
λ 9.116 X 10-8 m
 EXERCISE
Question…….
Calculate the wavelengths and frequencies of the
photons associated with the following electronic transition

(i) n2 to n1 ( ANSWER λ= 121.5 x 10 m, ν = 2.47 x 10 Hz)

-9 15

(ii) n4 to n1 (ANSWER λ =9.72 x 10

-9 m, ν =3.08 x 1016 Hz)
(iii)n4 to n2 (ANSWER λ =4.86 x 10
-8 m, ν =6.17 x 10 15 Hz)
 EXERCISE

In a particular electronic transition, photons with the

frequency of 5.11 x 10 13 Hz are emitted. Calculate the
difference in energy (in kJ mol-1) between the two levels
involved (ANSWER : 20.4 kJmol-1)
 Significance of Atomic Spectra
➲In Lyman series, the frequency of the convergence of spectral lines can
be used to find the ionisation energy of hydrogen atom:
IE = hν
(v =Frequency last line)

➲The frequency of the first line of the Lyman series > the frequency of
the first line of the Balmer series.

IE
Line ∆E, ν
spectrum λ
Balmer Series Lyman Series
 IONIZATION ENERGY OF H ATOM

Ionization energy (IE) :

‘minimum energy needed to remove of 1 mol of
electrons from 1 mol of gaseous atoms or ions’

Unit: kJ/mol
H(g) → H+(g) + e
nf = ∞ ni = 1 ∆E = ?

∆E = Efinal – Einitial = RH ( 1 1)
n2 n2
i f
 EXAMPLE

Calculate the ionization energy of H atom in kJmol-1.

 Answer
Complete removal of an electron from an H atom:
H(g) → H+(g) + e ∆E = ?
Electron transition: ni = 1 (ground state)
nf = ∞ (complete removal)
1 1
∆ E = RH
n2i n2f

= 2.18 x 10-18 J x 1 1
12 ∞2

= 2.18 x 10-18 J x 1 0 = 2.18 x 10-18 J

12 (for removal of one electron form one H atom)
 Ans:
EXAMPLE
EXAMPLE
Ans: –– 14
EXAMPLE 14 – 14
EXAMPLE

For removal of 1 mol electrons from 1 mol H atom:

2.18 x 10-18 J 6.02 x 1023 atoms H

∆E = x
1 atom H 1 mol

= 1.3124 x 106 J/mol

= 1312.4 kJ/mol
 Example
EXAMPLE

10.97 10.66 10.52 10.27 9.74 8.22

wave number (x106 m-1)

The Lyman series of the spectrum of

hydrogen is shown above. Calculate the
ionisation energy of hydrogen from the
spectrum.
 Solution Ans: EXAMPLE

ΔE = hc/λ
=h x c / λ = h x c x (1/ λ)
= 6.626 x 10-34 J s x 3 x 108 m s-1 x 10.97x 106 m-1
= 218.06x 10-20 J
= 2.18 x 10-18 J

Ionisation energy = ΔE x NA
IE = 2.18 X 10 -18x 6.02 X 1023 J mol-1
=1.312 x 106 J mol-1
= 1312 kJ mol-1
Ionisation energy

Convergent limit 1 st line

Ionisation energy is determined by detecting

the wavelength of the convergence point
 The Bohr’s Theory

➲Bohr was successful in introducing the idea of quantum energy and in

explaining the lines of hydrogen spectrum.

➲Histheory could not be extended to predict the energy levels

and spectra of atoms and ions with more than one electron.

➲Histheory can only explain the hydrogen spectrum or ions

contain one electron system (Eg: He+, Li2+)

➲Modern quantum mechanics retain Bohr’s concept of discrete energy

states and energy involved during transition of electrons but totally
reject the circular orbits he introduced.
The weakness of Bohr’s Theory

a) electrons are restricted to orbit

the nucleus at certain fixed distance

b) it cannot explain for the dual nature of electron

c) it cannot explain for the extra lines formed in

the hydrogen spectrum

d) it cannot explain the spectra of atom with more

than one electron
 LIMITATION OF BOHR MODEL
Success in explaining the spectral line of
H atom but not other atoms

It works for one–electron species such

as H atom, He+(Z=2), Li2+(Z=3), Be3+(Z=4),
B4+(Z=5), C5+(Z=6), N6+(Z=7) and O7+(Z=8)
The model does not work for atoms > one electrons

Electrons do not travel in fixed orbit as we imagine before

X
Additional nucleus–electron attraction and
electron–electron repulsion
 3.1-49

Electrons movement is far less clearly defined

Where 90% of the

e- density is found
for the 1s orbital

We cannot assign fixed path

for electrons, such as circular
orbits of Bohr’s model!
 Point to Ponder

Davisson & Germer observed the diffraction of electrons when a

beam of electrons was directed at a nickel crystal. Diffraction
patterns produced by scattering electrons from crystals are very
similar to those produced by scattering X-rays from crystals. This
experiment demonstrated that electrons do indeed possess
wavelike properties.
Thus, can the ‘position’ of a wave be specified???
 de Broglie’s Postulate

In 1924 Louis de Broglie proposed that not only light but all
matter has a dual nature and possesses both wave and
particles properties. De Broglie deduced that the particle and
wave properties are related by the expression:

h = Planck constant (J s)
m = particle mass (kg)
μ = velocity (m/s)
λ = wavelength of a matter wave
Electron Motion Around Atom
Shown as a de Broglie Wave

e
 Heisenberg’s Uncertainty Principle

It is impossible to know simultaneously both the momentum p

(defined as mass times velocity) and the position of a particle
in exactly in certain time.

Stated mathematically,

where ∆x = uncertainty in measuring the position

∆ p = uncertainty in measuring the momentum
= ∆ mv
h = Planck constant